DESC:FIELD OF THE INVENTION
The present invention relates to a synergistic agrochemical composition for controlling pests. More particularly, the present invention relates to an insecticidal composition comprising at least one Phenyl Pyrazole, at least one Neonicotinoid, Pymetrozine, and a process of preparation thereof.

BACKGROUND OF THE INVENTION
Crop losses caused by insect pests are quite high in developed and developing countries. Approximately 20 to 40% of global crop production is lost to pests annually. According to the Food and Agriculture Organization of the United Nations, plant diseases cost the global economy around $220 billion each year, and invasive insects around $70 billion. Pesticides are used to manage pests, dangerous insects, and several plant diseases afflicting farm crops.

Rice (Oryza sativa L.) is one of the world's most important staple food crops, providing food for nearly half of the global population. India is one of the major rice growing countries, and it leads the world with an area of 43.38 million hectares and a production of 104.32 million tonnes. Agricultural crops are vulnerable to attack by more than 100 species of insects; 15 to 20 can cause economic damage and cause 21 to 51 per cent yield loss. The sucking insect pests, brown planthopper (BPH), Nilaparvata lugens (Stål) and whitebacked planthopper (WBPH), Sogatella furcifera (Horvath) of the order Homoptera and family Delphacidae are the economically most important pests of rice crop (Singh et al., 2002).

During recent periods, the sucking pest complex has evolved as a major headache for cotton growing farmers, including the Bt cotton, which was also affected by such pests. According to an estimate, bollworms and sucking pest complex cause about 20-40% yield losses. Important sucking insect pests are jassid Amarasca devastans Dist. (Hemiptera: Cicadellidae), whitefly, Bemisia tabaci (Genn.) (Hemiptera: Aleyrodidae), cotton thrips, Thrips tabaci Lind. (Thysanoptera: Thripidae) and cotton aphid, Aphis gossypii Glover (Hompotera: Aphididae). No single pest control method is sufficient for good production. Effective control of cotton pests, cotton yield can be increased by 200-300 kg ha-1. Planthopper damage also leads to transmission of viral plant diseases like grassy stunt and wilted stunt. A severe attack may cause “hopper burn” symptoms in the field.

Farmers mostly rely on insecticides for their pest management. However, the indiscriminate use of insecticides has led to many problems, such as elimination of natural predators, environmental pollution, resistance and resurgence. Continuous use of single or binary insecticides has led to the evolution of insecticide resistance in most pests, including BPH and WBPH in Asia. Thus, more concentrated formulations are applied, which leads to a high risk of toxicity to humans and the environment and an increased risk of resistance in plants.

There is a need to explore the possibility of utilizing a highly effective combination of insecticides, particularly combinations of those with different and novel modes of action that can fit idyllically in the IPM programme against pests, including hoppers in the rice agroecosystem. However, due to the different structures and properties of different actives, formulating a composition of two or more actives has numerous challenges, such as compatibility, viscosity, flowabilty, suspensibility, particle size, stability and shelf life.

Thus, there still exists a need to develop pesticidal compositions having a broad scope of activity and a synergistic effect, as well as overcome the problem of viscosity, flowability, stability and particle size to avoid or control the development of resistant strains to the active ingredients/compounds while minimizing the doses of the actives. Further, it is essential that the composition is environmentally safe and reduces the cost of the treatment. The composition should be synergistic and storage stable, safely packed and ready-to-use.

OBJECTIVE OF THE INVENTION

The primary objective of the invention is to provide a synergistic composition comprising at least three insecticides.

Another objective of the present invention is to provide an insecticidal composition with enhanced efficacy and crop yield without phytotoxicity.

Another objective of the present invention is to provide a process for the preparation of the synergistic composition.

Another objective of the present invention is to provide a synergistic composition comprising at least one Phenyl pyrazole, at least one Neonicotinoid, Pymetrozine.

Another objective of the present invention is to provide a synergistic composition with broad spectrum control of pests.

Another objective of the present invention is to provide a method for controlling pests in the agricultural field.

The above and other objectives of the present invention are achieved according to the following embodiments of the present invention. However, the disclosed embodiments are exemplary based on the preferred and best mode of the invention and not limit the scope of the present invention.

SUMMARY OF THE INVENTION

Accordingly, the present invention aims to provide a synergistic insecticidal composition comprising at least one Phenyl pyrazole, at least one Neonicotinoid, Pymetrozine, and the process of preparation thereof.

In another aspect, the present invention provides a process for preparing the synergistic composition comprising at least one Phenyl pyrazole, at least one Neonicotinoid, and Pymetrozine.

In accordance with one aspect of the present invention, there is provided a synergistic composition for crop production management comprising of fipronil in an amount in the range of 1-80% by weight, dinotefuran in an amount in the range of 0.5-85% by weight, pymetrozine in an amount in the range of 5-70% by weight, and 0.1 to 50% of agriculturally acceptable adjuvant.

In another aspect, the synergistic composition of the present invention may be formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

In another aspect of the present invention, the synergistic composition comprises one or more inactive excipients selected from the group comprising of a carrier(s), surfactant(s), binder(s), disintegrating agent(s), dispersants or dispersing agent(s), wetting agent(s), pH modifier(s), thickener(s), biocide(s), preservative(s), anti-freezing agent(s), defoamer(s), solvents, water soluble polymers, and/or stabilizer(s) or a combination thereof.
In accordance with another aspect of the present invention, there is provided a synergistic composition for crop production management comprising of fipronil in an amount in the range of 1 to 80% by weight, dinotefuran in an amount in the range of 0.5-85% by weight, and pymetrozine in an amount in the range of 5-70% by weight, 0.1-50 % of agriculturally acceptable adjuvant, wherein the resultant composition is non-toxic, efficient suspension concentrate formulation.

In another aspect, the synergistic composition comprises water-soluble polymers in an amount in the range of 1 - 15% w/w.

These and other objectives and embodiments of the invention will become more fully apparent when the following detailed description is read with the accompanying study details and examples. However, both the foregoing summary of the invention and the following detailed description of it represent one potential experiment and embodiment and are not restrictive of the invention or other alternate embodiments of the invention.

DESCRIPTION OF THE INVENTION
The definitions provided herein below for the terminologies used in the present disclosure are for illustrative purpose only and in no manner limit, the scope of the present invention disclosed in the present disclosure.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Other process and materials similar, or equivalent, to those described herein may be used in the practice of the present invention.

It is to be noted that, as used in the specification, the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.

The term “formulation” and “composition” as used herein convey the same meaning and may be used interchangeably.

The expression of various quantities in terms of “% w/w” or “%” means the percentage by weight relative to the weight of the total solution or composition unless otherwise specified.

The term “synergistic”, as used herein, refers to the combined action of two or more active agents blended together and administered conjointly that is greater than the sum of their individual effects.

The term “active ingredient” (a.i.) or “active agent” used herein refers to that component of the composition responsible for the control of insect pests.

The term “crop” shall include a multitude of desired crop plants or individual crop plants. The term “control” means to inhibit the ability of pests to survive, grow, feed and/or reproduce or to limit the pests’ related damage or loss in crop plants. To “control” pests may or may not mean killing the insects, although it may mean killing the pests.

As used herein, the term “insecticide” refers to any chemical substance used to destroy/kill, inhibit or otherwise adversely affect insect pests.

As used herein, the term “Pymetrozine” encompasses its agrochemically acceptable salt(s), derivative(s) or any other modified form of Pymetrozine.
As used herein, the term “Fipronil” encompasses its agro-chemically acceptable salt(s), derivative(s) or any other modified form of Fipronil.

As used herein, the term “Dinotefuran” encompasses its agro-chemically acceptable salt(s), derivative(s) or any other modified form of Dinotefuran.

As used herein, the term “water soluble polymer” encompasses all organic macromolecules derived from natural sources that can dissolve, disperse, or swell in water.

Accordingly, the present invention provides a synergistic insecticidal composition comprising at least one Phenyl pyrazole, at least one Neonicotinoid, Pymetrozine, and water-soluble polymer and a process for preparing it.

In an exemplary embodiment, the present invention provides a synergistic insecticidal composition comprising of fipronil, at least one neonicotinoid, and pymetrozine.

In another exemplary embodiment, the present invention provides a synergistic insecticidal composition comprising of fipronil, at least one neonicotinoid, pymetrozine, water soluble polymer and at least one inactive excipient.

In an embodiment of the present invention, the water soluble polymer may be obtained from natural sources. Examples of water soluble polymer include but not limited to Lignosulfonates, Poly [di (carboxylatophenoxy) phosphazene] (PCPP), Poly[di(methoxyethoxy) phosphazene], Carboxypolymethylene (carbomer, carbopol), Cellulose derivatives, ethyl methylcellulose, methylcellulose, and sodium carboxymethyl cellulose, Acacia gum, Alginates, Dextran, Polyvinyl pyrrolidone (PVP), Polyethylene glycol (PEG), Poly (methacrylic acid) sodium salt, Poly (methacrylic acid) ammonium salt, Poly(maleic acid), Poly (styrene sulfonic acid), sodium salt, Poly (styrene sulfonic acid), Poly (N-vinylpyrrolidone/vinyl acetate), Poly(vinyl acetate), Poly(N-vinylpyrrolidone), Poly(vinyl methyl ether), Poly(ethylene oxide), Poly (oxyethylene) sorbitan monolaurate (Tween 20), Poly(vinyl alcohol), Poly(l-lysine hydrobromide), Polyacrylamide, Poloxamer or combination thereof.

In an embodiment, the synergistic insecticidal composition comprises lignosulfonate selected from but limited to calcium lignosulfonate, sodium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate or a combination thereof.

In another exemplary embodiment, the present invention provides a synergistic insecticidal composition comprising of fipronil, dinotefuran, pymetrozine, and lignosulfonate.

In another exemplary embodiment, the present invention provides a synergistic insecticidal composition comprising of fipronil, dinotefuran, pymetrozine, sodium lignosulfonate and at least one inactive excipient.

In another exemplary embodiment, the composition according to the present invention comprises at least one Phenyl pyrazole in an amount in the range of 1 - 80% by weight, at least one Neonicotinoid in an amount in the range of 0.5 - 85%% by weight, pymetrozine in an amount in the range of 5 - 70% by weight and water-soluble polymer in an amount in the range of 1 - 15% by weight.

The inventors have surprisingly found that the composition at the aforementioned weight percentage ranges provides a synergistic effect.

In another exemplary embodiment, the present invention provides a synergistic insecticidal composition comprising of fipronil in an amount in the range of 1-80% by weight, dinotefuran in an amount in the range of 0.5-85% by weight, pymetrozine in an amount in the range of 5-70% by weight and lignosulfonate in an amount in the range of 1 - 15% by weight.

In another exemplary embodiment, the present invention provides a synergistic insecticidal composition comprising fipronil in an amount in the range of 1-50% by weight, dinotefuran in an amount in the range of 5-50% by weight, pymetrozine in an amount in the range of 5-50% by weight and sodium lignosulfonate in an amount in the range of 1 - 15% by weight.

In another exemplary embodiment, the synergistic composition of the present invention may be formulated as Capsule suspension (CS), Dispersible concentrate (DC), Dustable powder (DP), Powder for dry seed treatment (DS), Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquid, Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

In another embodiment of the present invention, the synergistic composition may comprise one or more inactive excipients selected from the group comprising of carrier(s), surfactant(s), binder(s), disintegrating agent(s), dispersants or dispersing agent(s), wetting agents, pH modifier(s), thickener(s), biocide(s), Preservative(s), anti-freezing agent(s), defoamer(s), solvents, and/or stabilizer(s) or a combination thereof.
In accordance with another embodiment of the present invention, the synergistic insecticidal composition comprises of fipronil in an amount in the range of 1-80% by weight, dinotefuran in an amount in the range of 0.5 - 85% by weight, and pymetrozine in an amount in the range of 5-70% by weight, sodium lignosulfonate in an amount in the range of 1 - 15% by weight, 0.1 - 50 % of agriculturally acceptable adjuvant, wherein the composition is non-toxic, efficient suspension concentrate formulation.

In accordance with another embodiment of the present invention, there is provided a synergistic composition for crop production management comprising of fipronil in an amount in the range of 1-80% by weight, dinotefuran in an amount in the range of 0.5-85% by weight, and pymetrozine in an amount in the range of 5-70% by weight, sodium lignosulfonate in an amount in the range of 1-15% by weight, 0.1-25% of dispersing agent, 2-25% Wetting and Dispersing agents, 0.1-25% anti-freezing agent, 0.1-50% of agriculturally acceptable adjuvant, wherein the composition is formulated as a stable suspension concentrate formulation.

A dispersant, also known as a dispersing agent, is a substance that adsorbs onto the surface of particles, preserving their dispersion and preventing them from re-aggregating. Dispersants are added to agrochemical formulations to aid in particle dispersion and suspension during manufacturing and to ensure particles re-disperse in water in a spray tank. They are a common ingredient in wettable powders, suspension concentrates, and water-dispersible granules. Surfactants used as dispersants have the ability to strongly adsorb onto a particle surface and offer a charged or steric barrier to particle re-aggregation. Surfactants that are often employed are anionic, non-ionic, or mixes of the two. Sodium lingo sulfonates are the most often used dispersants in wettable powder compositions.

Dispersing agent(s) may be selected from the group comprising of, but not limited to Acrylic Co-Polymer Solution, Alcohols, C9-11-iso-, C10-rich, ethoxylated.

Anti-freezing agent(s) may be selected from the group comprising of, but not limited to, glycols, mono-ethylene glycol, di-ethylene glycol, propylene glycol, polyethylene glycols, methoxy polyethylene glycols, polypropylene glycols, polybutylene glycols, glycerine and ethylene glycol. Water-based formulations often cause foam during mixing operations in production. In order to reduce the tendency of foaming; anti-foaming agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foaming agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane while the nonsilicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.

Antifoaming agent(s) may be selected from the group comprising of, but not limited to silicon emulsion based anti-foam agents, Siloxane polyalkyleneoxide, Polydimethyl Siloxane, trisiloxane ethoxylates and mixtures thereof.

Wetting agent(s) may be selected from the group comprising of, but not limited to alcohols, C9-11-iso-, C10-rich, ethoxylated.

Thickener(s) may be selected from the group comprising of, but not limited to, water-soluble polymer and inorganic fine powder, wherein water-soluble polymers such as xanthan gum, welan gum, guar gum, polyvinyl alcohol, carboxy methylcellulose, polyvinyl pyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative or a polysaccharide; or an inorganic fine powder selected from high purity silica, bentonite, white carbon. These thickeners may be used alone or in combination thereof.

Preservative may be selected from the group comprising of, but not limited to, a 20% aqueous dipropylene glycol solution of 1, 2-benzisothiazolin-3-one, formaldehyde potassium sorbate, 4-hydroxybenzoic acid esters, 2-methyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one.

Solvent(s) may be selected from the group comprising of, but not limited to, water, demineralized water (DM); alcohols such as ethanol, propanol, n-octanol, isopropanol ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerine; polyol ethers such as ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethers such as dipropyl ether, dioxane, tetrahydrofuran; aliphatic hydrocarbons such as normal paraffin, isoparaffin, kerosene, mineral oil; aromatic hydrocarbons such as xylene, toluene, naphthalene, solvent naphtha, solvent C9, solvent C10, solvent C12, solvesso 100, solvesso 150, solvesso 200; chlorinated aliphatic or aromatic hydrocarbons such as chloro benzene, chloro ethylene, methylene chloride; esters such as ethyl acetate, diisopropyl phthalate, dimethyl adipate, methyl oleate, methyl tallowate; lactones such as gamma-butyrolactone; amides such as dimethyl formamide, N-methyl-2-pyrrolidone, N-octyl pyrolidone, N, N dimethyl decanamide; nitriles such as acetonitrile; organo sulfur compounds.

In another embodiment of the present invention, the synergistic insecticidal composition comprises 14.8 % w/w of pymetrozine, 7 % w/w of fipronil, dinotefuran 4.8% w/w, and 5% of sodium lignosulfonate and excipients.

In another embodiment of the present invention, the synergistic insecticidal composition comprises 14.8 % w/w of pymetrozine, 7.5 % w/w of fipronil, dinotefuran 4.8% w/w, and 5% of calcium lignosulfonate and excipients.

In another embodiment of the present invention, the synergistic insecticidal composition comprises 14.8 % w/w of pymetrozine, 7 % w/w of fipronil, dinotefuran 4.8% w/w, and 5% of potassium lignosulfonate and excipients.

Below are the various examples for preparing different compounds according to the present invention. However, the below examples are not limited and will be further worked on within the scope of the current invention and filed:

Example 1: Suspension Concentrate (SC) Formulation
Table 1
S. No. INGREDIENTS QTY IN % W/W
1. Pymetrozine A.I 14.8
2. Fipronil A.I 7.0
3. Dinotefuran A. I 4.8
4. Dispersing agent - Acrylic Co-Polymer Solution 3.5
5. Wetting and Dispersing agents -Alcohols, C9-11-iso-, C10-rich, ethoxylated 0.5
6. Sodium lignosulfonate 5.0
7. Ant freezing agent- Propylene glycol 7
8. Silicon Defoamer 0.5
9. Xanthum Gum powder 0.10
10. 1,2-Benzisothiazolin-3- one @ 20 % as preservative 0.20
11. DM Water QS
TOTAL 100 gm

Manufacturing process:
1. Charge the pre feed mixing vessel with demineralized water (DM).
2. Add silicon defoamer and stir the premix.
3. Add the dispersion agent, wetting agent, and sodium lignosulfonate under stirring and mix for about 5 minutes.
4. Add pymetrozine, fipronil, and dinotefuran and mix and homogenize for 15 minutes.
5. Mill the mixture using a bead mill until the required particle size (preferably below 10 microns) is not obtained.
6. Transfer the milled material to a second post-feed vessel.
7. Add the xanthan gum solution, biocide, and remaining water quantity to the mixture.
8. Combine and homogenize the whole mixture using a homogenizer for about 20 minutes.
9. If there are any lumps of xanthan gum, increase the homogenization time for 5-10 minutes.
10. Pass the mixture through a normal sieve of 36 mesh if no lumps are observed and pack.
Table 2: Quality parameters of Suspension Concentrate (SC) formulation

S. No. Parameter Description
1. Physical state Viscous Liquid
2. Colour Beige to brown
3. Relative density (20ºC) 1.14 ± 0.1 g/ml @ 20°C
4. Suspensibility % w/w 80.00 min.
5. Degree of Dispersion % w/w Above 90 %
6. pH 1 % Aq. Solution 5.0 – 8.0
7. Flash point NA
8. Wet Sieve Test % w/w 98.0 % min.
9. Persistent Foam Max. 60 ml after 1 min.
10. Viscosity (Brookfield) at 100 RPM spindle 3 300-800 cps

Example 2a: Water dispersible Granules (WDG) Formulation

S. No. INGREDIENTS QTY

1 Pymetrozine Technical A.I. 37%
2 Fipronil Technical A.I. 15%
3 Dinotefuran Technical A.I. 13%
4 Linear Alcohol Derivative
Proprietary Blend 6%
5 Sodium lignosulfonate 8%
6 Lactose 5%
7 China Clay Q.S.

Example 2b: Water dispersible Granules (WDG) Formulation

S. No. INGREDIENTS QTY
1 Pymetrozine Technical AI 37%
2 Fipronil Technical AI 12%
3 Dinotefuron Technical AI 16%
4 Linear Alcohol Derivative
Proprietary Blend 6%
5 Sodium lignosulfonate 8%
6 Lactose 5%
7 China Clay Q.S.

Example 2c: Water dispersible Granules (WDG) Formulation

S. No. INGREDIENTS QTY
1 Pymetrozine Technical AI 37%
2 Fipronil Technical AI 20%
3 Dinotefuron Technical AI 8%
4 Linear Alcohol Derivative Proprietary Blend 6%
5 Sodium lignosulfonate 8%
6 Lactose 5%
7 China Clay Q.S.

MANUFACTURING PROCESS: -
1. Charge all raw materials, including technical, in the required quantity as per the recipe in the pre-blending vessel, and mix for at least 15 minutes.
2. Grind the mixture mass through milling.
3. Transfer the milled mass into a post blender and mix for 30 min.
4. Transfer a known quantity from the milled material and mix with water in a blender for 15 – 20 minutes.
5. Now transfer the mixed water powder quantity into the granulator and allow for granulation and then dry.
6. Now, draw the sample for analysis.

Comparative Examples:
Example 3
S. No Ingredients QTY (% w/w)
1. Pymetrozine Tech @ 96% 73.20
2. Fipronil Tech @ 95% 7.60
3. Dinotefuran @ 98% 5.10
4. Olefin sulfonate 8.00
5. Sodium Poly Naphthalene Formaldehyde Sulfonate 4.00
6. Lactose 2.1
TOTAL 100 gm

MANUFACTURING PROCESS:
1. Weighted all the technical ingredients and added olefin sulfonate and Sodium Poly Naphthalene Formaldehyde Sulfonate, then mixed them together;
2. Added lactose and mixed thoroughly;
3. Subjected the mixtures to jet milling;
4. Added water to make dough.

The resulting dough was extruded, but it was observed that the granules did not form well, and there were lumps during granulation. As a result, the product obtained was unstable and had low suspensibility, flowability, and compatibility. It is not possible to exclude water in the preparation of a water dispersible granule.

Example 4
S. No Ingredients QTY (% w/w)
1. Pymetrozine Tech @ 96% 2.40
2. Fipronil Tech @ 95% 84.50
3. Dinotefuran @ 98% 3.90
4. Olefin sulfonate 5.00
5. Sodium Poly Naphthalene Formaldehyde Sulfonate 3.00
6. Lactose 1.20
TOTAL 100 gm

MANUFACTURING PROCESS:
1. Weighted all the technical ingredients and added olefin sulfonate and Sodium Poly Naphthalene Formaldehyde Sulfonate, then mixed them together;
2. Added lactose and mixed thoroughly;
3. Subjected the mixtures to jet milling;
4. Added water to make dough.

The resulting dough was extruded, but no granules were formed, and the sieve got jammed. As a result, the product obtained was unstable and had low suspensibility, flowability, and compatibility. It is not possible to exclude water in preparing a water dispersible granule.

Example 5
S. No Ingredients QTY (% w/w)
1. Pymetrozine Tech @ 96% 2.20
2. Fipronil Tech @ 95% 3.2
3. Dinotefuran @ 98% 87.0
4. Olefin sulfonate 3.00
5. Sodium Poly Naphthalene Formaldehyde Sulfonate 3.00
6. Lactose 1.60
TOTAL 100 gm

MANUFACTURING PROCESS:
1. Weighted all the technical ingredients and added olefin sulfonate and Sodium Poly Naphthalene Formaldehyde Sulfonate, then mixed them together;
2. Added lactose and mixed thoroughly;
3. Subjected the mixtures to jet milling;
4. Added water to make dough.

The resulting dough was extruded, but no granules were formed, only dust obtained during granulation. As a result, the product obtained was unstable and had low suspensibility, flowability, and compatibility. It is not possible to exclude water in preparing a water dispersible granule.

Synergy Study
The following formula was used to calculate the expected activity of three-way combinations containing active ingredients, A, B and C:
Expected E = X+ Y + Z - (XY + XZ + YZ) + XYZ
100 10,000
X = growth as a percent-of-control with pymetrozine.
Y = growth as a percent-of-control with fipronil.
Z = growth as a percent-of-control with dinotefuran.
E = expected growth as a percent-of-control with insecticides.
Ratio = Observed Control %/Expected Control %
Ratio of O/E > 1, means synergism observed.

Example 6: Field evaluation of the bio efficacy of the present Insecticidal composition against paddy BPH.

Experiment Details

Season Kharif 2023
Location Basapattana (Gangavathi)
Crop Paddy
Age of Crop 60 days
Temperature Range during Trial 25 to 30?
Variety Kaveri sona
Single plot size 5x5 (25 m2)
Date of Transplanting/Sowing 07/08/2023
Number of sprays 1
Date of Sprays 07/10/2023
Target Pest Brown Planthopper (BPH)

Treatment Details:
S. No. Treatments Active Ingredient (AI) (gm/ha) Dose (ml or gm/ha) Water volume in L/ha
T1 Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7% SC 129.5+42+61.25 875 500
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 42+129.5 210 + 259 500
T3 Dinotefuran 20% SG + Fipronil 5% SC 42+61.25 210 + 1225 500
T4 Pymetrozine 50% WG + Fipronil 5% SC 129.5+61.25 259 + 1225 500
T5 Pymetrozine 50% WG 129.5 259 500
T6 Dinotefuran 20% SG 42 210 500
T7 Fipronil 5% SC 61.25 1225 500
T8 Control Nil Nil Nil

Methodology:
The experiment was laid out in randomized block design (RBD) with 3 replications and a single plot area of 25 m2. As per the treatment schedule, the test samples were applied at pest appearance using 500 litres of water per hectare using a knapsack sprayer.

Observation:
Pre-counts were taken prior to the spray conduction. Pests count (Area of observation- selected 5 hills per treatment and recorded population of BPH for each hill. After the spray population count was taken at 3, 7 and 15 days after application, respectively.

Results:
The BPH population ranged from 30 to 33 numbers per hill prior to treatments. The mean BPH population was the lowest in T1 (Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC) (875 ml/ha) treated plots, recording 91.31% reduction over control on 3 days after the spray. Percent reduction over control 7DAA was recorded highest in T1- Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC (96.86%).

Table 3: Effectiveness of different insecticides against paddy Brown Planthopper (BPH)
S. No. Treatments Dose g or ml/ha Effectiveness of different insecticide against Paddy BPH
Avg. Pre-count/ hill Percent (%) reduction over control
3DAA 7DAA 15DAA
T1 Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC 875 32.8 91.31 96.86 94.97
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 210 + 259 32.8 84.47 86.94 87.06
T3 Dinotefuran 20% SG + Fipronil 5% SC 210 + 1225 31.87 81.33 79.65 76.50
T4 Pymetrozine 50% WG + Fipronil 5% SC 259 + 1225 31.73 80.78 81.32 77.64
T5 Pymetrozine 50% WG 259 32.47 67.84 78.68 75
T6 Dinotefuran 20% SG 210 32.33 70.79 69.92 67.21
T7 Fipronil 5% SC 1225 32.8 47.87 45.12 42.96
T8 Control Nil 30.6 0 0 0

Table 4: Synergistic effect of different insecticides against paddy (BPH) 7DAA

Sno.

Treatment details Dose (ml or gm/ha) % Reduction
over control of paddy brown planthopper (BPH) 7DAA
Observed Expected Ratio Synergy
T1 Pymetrozine 14.8 % + Dinotefuran 4.8 % + Fipronil 7 % SC 875 96.86 46.84 2.07 Yes
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 210 + 259 86.94 93.59 0.93 No
T3 Dinotefuran 20% SG + Fipronil 5% SC 210 + 1225 79.65 83.49 0.95 No
T4 Pymetrozine 50% WG + Fipronil 5% SC 259 + 1225 81.32 88.3 0.92 No
T5 Pymetrozine 50% WG 259 78.68 _ _ _
T6 Dinotefuran 20% SG 210 69.92 _ _ _
T7 Fipronil 5% SC 1225 45.12 _ _ _
T8 Control Nil _ _ _ _

An overview of the results indicated that among all the treated insecticides, the highest percent reduction over control was recorded in T1-Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC -875ml/ha, with a significant 96.86 % reduction over control at 7DAA. It also demonstrated an impressive knockdown effect. Even At 15 DAA, the highest control was observed in T1.

Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC showed excellent knockdown as well as longer duration of control against Paddy BPH/WBPH.

Example 7: Field evaluation of the bio efficacy of the present Insecticidal composition against against cotton Jassids:

Season Kharif 2023
Location Khargone (MP)
Crop Cotton
Age of Crop 55 days
Temperature Range during Trial 25 to 30?
Variety Asha 1
Single plot size 5x5 (25 m2)
Date of Transplanting/Sowing 16/06/2023
Number of sprays 1
Date of Sprays 09/08/2023
Target Pest Jassids

Treatment Detail:

S. No. Treatments Active Ingredient (AI) (gm/ha) Dose (ml or gm/ha) Water volume in L/ha
T1 Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7% SC 129.5+42+61.25 875 500
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 42+129.5 210 + 259 500
T3 Dinotefuran 20% SG + Fipronil 5% SC 42+61.25 210 + 1225 500
T4 Pymetrozine 50% WG + Fipronil 5% SC 129.5+61.25 259 + 1225 500
T5 Pymetrozine 50% WG 129.5 259 500
T6 Dinotefuran 20% SG 42 210 500
T7 Fipronil 5% SC 61.25 1225 500
T8 Control Nil Nil Nil

Methodology
The experiment was conducted under field conditions at Khargone, Madhya Pradesh on cotton hybrid “Asha 1”. The experiment was laid out in RBD with 3 replications of each treatment with a single plot area of 25 m2, 5 plants were tagged per treatment and pest count taken prior to the application and the test sample as per the treatment scheduled were applied at pest appearance by using 500 litre of water ha-1 using a knapsack sprayer?fitted with hollow cone nozzle.

Observation:
Pre-counts were taken prior to the spray conduction Pest’s count (Area of observation- selected 5 plants per treatment, counted number of jassids per leaf. After the spray, population count was taken at 3, 7 and 15 days after application.

Result:
The data recorded revealed that pest population of jassids before the insecticidal application remained uniform throughout the experiment area. The observation day before spray showed that Jassid populations ranged between 3.07 – 3.40 per plant, respectively, and there was no significant difference among all the treatments before spray. However, after 3 DAA all the treatments showed significant difference in the population of Jassids compared to untreated control plot. Amongst all the treatments, T1- Pymetrozine 14.8 % + Dinotefuran 4.8 % + Fipronil 7 % SC (875 ml/ha) was found most effective for the reduction of Jassids population.

Table 5: Effectiveness of different insecticides against cotton jassids (Percent (%) reduction over control)

S. No. Treatments Dose g or ml/ha

Avg. Pre count per 3 leaves/plant
Percent (%) reduction over control
3 DAA 7 DAA 10 DAA
T1 Pymetrozine 14.8 % + Dinotefuran 4.8 % + Fipronil 7 % SC 875 3.07 96.36 98.36 97.4
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 210 + 259 3.27 92.73 93.44 92.21
T3 Dinotefuran 20% SG + Fipronil 5% SC 210 + 1225 3.33 63.64 65.57 61.04
T4 Pymetrozine 50% SG + Fipronil 5% SC 259 + 1225 3.40 53.64 45.90 41.99
T5 Pymetrozine 50% WG 259 3.20 47.27 40.98 33.77
T6 Dinotefuran 20% SG 210 3.07 58.18 54.1 53.25
T7 Fipronil 5% SC 1225 3.13 41.82 37.7 33.77
T8 Control Nil 3.27 0 0 0

Table 6: Synergistic effect of different insecticides against cotton jassids 7DAA
S. No. Treatment details Dose (ml or gm/ha) % Reduction
over control of cotton jassids 7DAA
Observed Expected Ratio Synergy
T1 Pymetrozine 14.8 % + Dinotefuran 4.8 % + Fipronil 7 % SC 875 98.36 66.41 1.48 Yes
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 210 + 259 93.44 72.91 1.28 Yes
T3 Dinotefuran 20% SG + Fipronil 5% SC 210 + 1225 65.57 71.40 0.92 No
T4 Pymetrozine 50% WG + Fipronil 5% SC 259 + 1225 45.90 63.23 0.73 No
T5 Pymetrozine 50% WG 259 40.98 _ _ _
T6 Dinotefuran 20% SG 210 54.1 _ _ _
T7 Fipronil 5% SC 1225 37.7 _ _ _
T8 Control Nil _ _ _ _

Conclusion:
The above results indicate that among all the treatments, highest percent reduction over control (% ROC) was observed in Pymetrozine 14.8 % + Dinotefuran 4.8 % + Fipronil 7 % SC (875 ml/ha), which was found to be the most effective for the reducing the jassids population. There were no phytotoxicity symptoms on the crop at the recommended application dose in the experiment.

Example 8: Field evaluation of the bio efficacy of the present Insecticidal composition against against cotton Thrips:

Season Kharif 2023
Location Aurangabad (Maharashtra)
Crop Cotton
Age of Crop 54 days
Temperature Range during Trial 20 to 30?
Variety RCH659
Single plot size 5x5 (25 m2)
Date of Transplanting/Sowing 19/06/2023
Number of sprays 1
Date of Sprays 12/08/2023
Target Pest Thrips

Treatment Detail:

S. No. Treatments Active Ingredient (AI) (gm/ha) Dose (ml or gm/ha) Water volume in L/ha
T1 Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7% SC 129.5+42+61.25 875 500
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 42+129.5 210 + 259 500
T3 Dinotefuran 20% SG + Fipronil 5% SC 42+61.25 210 + 1225 500
T4 Pymetrozine 50% WG + Fipronil 5% SC 129.5+61.25 259 + 1225 500
T5 Pymetrozine 50% WG 129.5 259 500
T6 Dinotefuran 20% SG 42 210 500
T7 Fipronil 5% SC 61.25 1225 500
T8 Control Nil Nil Nil

Methodology
The experiment was conducted under field conditions at Aurangabad, Maharashtra on cotton hybrid “RCH659”. The experiment was laid out in RBD with 3 replications of each treatment with a single plot area of 25 m2, 5 plants were tagged per treatment and pest count taken prior to the application and the test sample as per the treatment scheduled were applied at pest appearance by using 500 litre of water ha-1 using a knapsack sprayer?fitted with hollow cone nozzle.

Observation:
Pre-counts were taken prior to the spray application Pest’s count (Area of observation- selected 5 plants per treatment, counted number of Thrips per leaf. After the spray, population count was taken at 3, 7 and 15 days after application.

Result:
The data recorded revealed that before insecticidal applications the population of Thrips remained uniform throughout the trial plot. The observation day before spray showed that Thrips populations ranged between 5.47-5.93 per plant, respectively, and there was no significant difference among all the treatments. However, after 3 days of application all the treatments showed significant difference in the population of Thrips compared to control. Amongst all the treatments, T1- Pymetrozine 14.8 % + Dinotefuran 4.8 % + Fipronil 7 % SC (875 ml/ha) was the most effective for the reduction of Thrips population.

Table 7: Effectiveness of different insecticides against cotton thrips (Percent (%) reduction over control)
S. No. Treatments
Dose (ml or gm/ha) Avg. Pre count per 3 leaves per plant Percent (%) reduction over control
3 DAA 7DAA 10DAA
T1 Pymetrozine 14.8 % + Dinotefuran 4.8 % + Fipronil 7 % SC 875 5.80 72.08 74.67 69.93
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 210 + 259 5.73 58.44 60.67 54.55
T3 Dinotefuran 20% SG + Fipronil 5% SC 210 + 1225 5.87 62.34 68.00 62.24
T4 Pymetrozine 50% WG + Fipronil 5% SC 259 + 1225 5.47 61.04 67.33 61.54
T5 Pymetrozine 50% WG 259 5.87 38.96 40.00 33.57
T6 Dinotefuran 20% SG 210 5.53 50.65 53.33 51.75
T7 Fipronil 5% SC 1225 5.87 55.19 55.33 49.65
T8 Control Nil 5.93 0 0 0

Table 8: Synergistic effect of different insecticides against cotton thrips

S. No. Treatment details Dose (ml or gm/ha) % Reduction over control of cotton thrips 7DAA
Observed Expected Ratio Synergy
T1 Pymetrozine 14.8 % + Dinotefuran 4.8 % + Fipronil 7 % SC 875 74.67 63.90 1.17 Yes
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 210 + 259 60.67 71.98 0.84 No
T3 Dinotefuran 20% SG + Fipronil 5% SC 210 + 1225 68.00 79.13 0.86 No
T4 Pymetrozine 50% WG + Fipronil 5% SC 259 + 1225 67.33 73.18 0.92 No
T5 Pymetrozine 50% WG 259 40.00 _ _ _
T6 Dinotefuran 20% SG 210 53.33 _ _ _
T7 Fipronil 5% SC 1225 55.33 _ _ _
T8 Control Nil 0 _ _ _

Conclusion:
The above results indicate that among all the treatments, highest percent reduction over control (% ROC) was observed in Pymetrozine 14.8 % + Dinotefuran 4.8 % + Fipronil 7 % SC (875 ml/ha), which was found to be the most effective for the reducing the Thrips population. There were no phytotoxicity symptoms on the crop at the recommended application dose in the experiment.

Example 9: Evaluation of phytotoxicity of the present Insecticidal composition:
Visual observations were recorded 3, 7, and 10 days after the application (DAA) of the tested product. The parameters observed were leaf injury on tip/surface, stunting, necrosis, chlorosis, vein clearing, epinasty, hyponasty, and wilting based on the 0-10 scale given in the table below. A total of 20 plants per plot were observed.

Table 9: Phytotoxicity symptoms scoring and rating for leaf injury on tip/surface
Leaf injury on tips /surface Rating
0% 0
1-10% 1
11-20% 2
21-30% 3
31-40% 4
41-50% 5
51-60% 6
61-70% 7
71-80% 8
81-90% 9
91-100% 10

Phytotoxicity studies:

Table 10: Phytotoxic effect of various treatments on Paddy after 3 DAA
S. No. Treatment details Dose (ml or gm/ha) 3DAA
L S N C V E H W
T1 Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC 875 0 0 0 0 0 0 0 0
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 210 + 259 0 0 0 0 0 0 0 0
T3 Dinotefuran 20% SG + Fipronil 5% 210 + 1225 0 0 0 0 0 0 0 0
T4 Pymetrozine 50% WG + Fipronil 5% SC 259 + 1225 0 0 0 0 0 0 0 0
T5 Pymetrozine 50% WG 259 0 0 0 0 0 0 0 0
T6 Dinotefuran 20% SG 210 0 0 0 0 0 0 0 0
T7 Fipronil 5% SC 1225 0 0 0 0 0 0 0 0
T8 Control Nil 0 0 0 0 0 0 0 0

DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting

Table 11: Phytotoxic effect of various treatments on Paddy after 7 DAA
S. No. Treatment details Dose (ml or gm/ha) 7DAA
L S N C V E H W
T1 Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC 875 0 0 0 0 0 0 0 0
T2 Dinotefuran 20% WG + Pymetrozine 50% WG 210 + 259 0 0 0 0 0 0 0 0
T3 Dinotefuran 20% WG + Fipronil 5% SC 210 + 1225 0 0 0 0 0 0 0 0
T4 Pymetrozine 50% WG + Fipronil 5% SC 259 + 1225 0 0 0 0 0 0 0 0
T5 Pymetrozine 50% WG 259 0 0 0 0 0 0 0 0
T6 Dinotefuran 20% SG 210 0 0 0 0 0 0 0 0
T7 Fipronil 5% SC 1225 0 0 0 0 0 0 0 0
T8 Control Nil 0 0 0 0 0 0 0 0

DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting

Table 12: Phytotoxic effect of various treatments on Paddy after 10 DAA
S. No. Treatment details Dose (ml or gm/ha) 10DAA
L S N C V E H W
T1 Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC 875 0 0 0 0 0 0 0 0
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 210 + 259 0 0 0 0 0 0 0 0
T3 Dinotefuran 20% SG + Fipronil 5% SC 210 + 1225 0 0 0 0 0 0 0 0
T4 Pymetrozine 50% WG + Fipronil 5% SC 259 + 1225 0 0 0 0 0 0 0 0
T5 Pymetrozine 50% WG 259 0 0 0 0 0 0 0 0
T6 Dinotefuran 20% SG 210 0 0 0 0 0 0 0 0
T7 Fipronil 5% SC 1225 0 0 0 0 0 0 0 0
T8 Control Nil 0 0 0 0 0 0 0 0

DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting

Results:
Tables 10, 11 and 12 indicate that application of Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC in all doses mentioned in the tables showed no phytotoxicity symptoms like leaf injury on tips, leaf injury on surface, wilting, vein clearing, necrosis, epinasty and hyponasty in paddy crop. Thus, applying Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC can be considered completely safe for paddy crops.

Table 13: Phytotoxic effect of various treatments on Cotton after 7 DAA
S. No. Treatments Dose (ml or gm/ha) 7DAA
L S N C V E H W
T1 Pymetrozine 14.8 % + Dinotefuran 4.8 % + Fipronil 7 % SC 875 0 0 0 0 0 0 0 0
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 210 + 259 0 0 0 0 0 0 0 0
T3 Dinotefuran 20% SG + Fipronil 5% SC 210 + 1225 0 0 0 0 0 0 0 0
T4 Pymetrozine 50% WG + Fipronil 5% SC 259 + 1225 0 0 0 0 0 0 0 0
T5 Pymetrozine 50% WG 259 0 0 0 0 0 0 0 0
T6 Dinotefuran 20% SG 210 0 0 0 0 0 0 0 0
T7 Fipronil 5% SC 1225 0 0 0 0 0 0 0 0
T8 Control Nil 0 0 0 0 0 0 0 0
DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting

Table 14: Phytotoxic effect of various treatments on Cotton after 10 DAA
S. No. Treatments Dose (ml or gm/ha) 10DAA
L S N C V E H W
T1 Pymetrozine 14.8 % + Dinotefuran 4.8 % + Fipronil 7 % SC 875 0 0 0 0 0 0 0 0
T2 Dinotefuran 20% SG + Pymetrozine 50% WG 210 + 259 0 0 0 0 0 0 0 0
T3 Dinotefuran 20% SG + Fipronil 5% SC 210 + 1225 0 0 0 0 0 0 0 0
T4 Pymetrozine 50% WG + Fipronil 5% SC 259 + 1225 0 0 0 0 0 0 0 0
T5 Pymetrozine 50% WG 259 0 0 0 0 0 0 0 0
T6 Dinotefuran 20% SG 210 0 0 0 0 0 0 0 0
T7 Fipronil 5% SC 1225 0 0 0 0 0 0 0 0
T8 Control Nil 0 0 0 0 0 0 0 0

DAA – Days after application, L-Leaf injury on tips/surface, S-stunting, N-Necrosis, C-Chlorosis, V- Vein clearing, E-Epinasty, H-Hyponasty, W-wilting

Results:
Tables 13 and 14 indicate that application of Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC in all doses mentioned in the table showed no phytotoxicity symptoms like leaf injury on tips, leaf injury on surface, wilting, vein clearing, necrosis, epinasty and hyponasty in paddy crop. Thus applying Pymetrozine 14.8 %+ Dinotefuran 4.8%+ Fipronil 7 % SC can be considered completely safe for cotton crops.

Example 10: Comparison of compositions with and without water soluble polymers.

Example 10a:
S. No. Comparative Composition
(without Sodium Lignosulfonate) Present Composition
(with Sodium Lignosulfonate)
1. 14.8% Pymetrozine A.I 14.8% Pymetrozine A.I
2. 8% Fipronil A.I 7.5% Fipronil A.I
3. 3.2% Dinotefuran A. I 4.8% Dinotefuran A. I
4. 3% Dispersing agent - Acrylic Co-Polymer Solution 3.5% Dispersing agent - Acrylic Co-Polymer Solution
5. 0.5% Wetting and Dispersing agents -Alcohols, C9-11-iso-, C10-rich, ethoxylated 0.5% Wetting and Dispersing agents -Alcohols, C9-11-iso-, C10-rich, ethoxylated
6. 2% Oxirane, methyl-,polymer with oxirane, monobutyl ether 5.0% Sodium lignosulfonate
7. 8% Ant freezing agent- Propylene glycol 7.0% Ant freezing agent- Propylene glycol
8. 0.5% Silicon Defoamer 0.5% Silicon Defoamer
9. 0.1% Xanthum Gum powder 0.10% Xanthum Gum powder
10. 0.15% 1,2-Benzisothiazolin-3- one @ 20 % as preservative 0.20% 1,2-Benzisothiazolin-3- one @ 20 % as preservative
11. QS. DM Water QS DM Water
Viscosity More than 900 cps 492 cps

Example 10b:
S. No. Comparative Composition
(without Calcium Lignosulfonate) Present Composition
(with Calcium Lignosulfonate)
1. 14.8% Pymetrozine A.I 14.8% Pymetrozine A.I
2. 8% Fipronil A.I 7.5% Fipronil A.I
3. 3.2% Dinotefuran A. I 4.8% Dinotefuran A. I
4. 3% Dispersing agent - Acrylic Co-Polymer Solution 3.5% Dispersing agent - Acrylic Co-Polymer Solution
5. 1.5% Ethoxylated Tristyrylphenol 0.5% Wetting and Dispersing agents -Alcohols, C9-11-iso-, C10-rich, ethoxylated
6. 2% Alcohols, C12-15, ethoxylated 5.0% Calcium lignosulfonate
7. 8% Ant freezing agent- Propylene glycol 7.0% Ant freezing agent- Propylene glycol
8. 0.5% Silicon Defoamer 0.5% Silicon Defoamer
9. 0.1% Xanthum Gum powder 0.10% Xanthum Gum powder
10. 0.15% 1,2-Benzisothiazolin-3- one @ 20 % as preservative 0.20% 1,2-Benzisothiazolin-3- one @ 20 % as preservative
11. QS. DM Water QS DM Water
Viscosity More than 1200 cps 497 cps

Examples 10a and 10b above show that comparative compositions without lignosulfonate either dissolve or undergo Ostwald Ripening and eventually sediment. Further, the composition (without lignosulfonate) forms gel-like structures, i.e., unstructured conglomerates of the active ingredient, which negatively influence the rheological properties, such as viscosity, or clog the spray nozzles. In contrast, the composition prepared per the present invention is highly stable, has a viscosity of 492 cps or 497 cps, and has a synergistic effect as per tables 3, 4, 5, 6, 7 and 8. There is a clear and significant enhancement that is not anticipated or expected.

Example 11:
The compositions prepared according to the present invention were investigated for suspensibility and degradation of active ingredients as well as its 15 effects on the stability of the composition. The stability study was conducted for zero days, 14 days AHS (Accelerated Heat Stability) at 54±2°C. Parameters such as suspensibility, wet sieve analysis and degradation of active ingredients were tested for 0 and 14 days, respectively. The results are summarized in Table 15.

Table 15
Storage Condition: 54 ? for 14 D in Hot Air Oven/ Stability Chambers
Test Parameter 0-day analysis 14-D Ambient 14- D 54 ?
Description Beige colour suspension Beige colour suspension Beige colour suspension
Active Ingredients
Pymetrozine 14.93 14.92 14.81
Fipronil 7.10 7.11 7.04
Dinotefuran 4.91 4.92 4.85
Suspensibility
Pymetrozine 96.38 95.28 93.77
Fipronil 92.32 91.29 90.12
Dinotefuran 99.2 99.6 99.9
pH 1 % Aq. Suspension 6.42 6.41 6.33
Viscosity s-3 100 RPM 25 ? 580 560 520
Wet Sieve 45 µ IS sieve <99 % <99 % <99 %
Particle Size D10 + D50 + D90 1.07 + 2.68 + 5.9 1.12 + 3.01 + 6.1 1.29 + 4.33 + 9.9

Thus, Table 15 above shows that degradation of the active compounds pymetrozine, fipronil, and dinotefuran in the composition was not observed when kept even at 54±2°C for 14 days. Also, the compositions of Example 1 and Example 2 were found to remain quite stable with negligible degradation when kept for real-time stability for 12 months. There was no significant change in the composition's suspensibility.

While the invention is amenable to various modifications and alternative forms, some embodiments have been illustrated by way of example in the drawings and are described in detail above. The intention, however, is not to limit the invention by those examples and the invention is intended to cover all modifications, equivalents, and alternatives to the embodiments described in this specification.

The embodiments in the specification are described in a progressive manner and the focus of description in each embodiment is the difference from other embodiments. For same or similar parts of each embodiment, reference may be made to each other.

It will be appreciated by those skilled in the art that the above description was in respect of preferred embodiments and that various alterations and modifications are possible within the broad scope of the appended claims without departing from the spirit of the invention with the necessary modifications.

Based on the description of disclosed embodiments, persons skilled in the art can implement or apply the present disclosure. Various modifications of the embodiments are apparent to persons skilled in the art, and general principles defined in the specification can be implemented in other embodiments without departing from the spirit or scope of the present disclosure. Therefore, the present disclosure is not limited to the embodiments in the specification but intends to cover the most extensive scope consistent with the principle and the novel features disclosed in the specification.
,CLAIMS:We Claim:

1. A synergistic insecticidal composition comprising:
a. pymetrozine;
b. fipronil;
c. dinotefuran;
d. at least one agriculturally acceptable excipient.

2. The composition as claimed in claim 1, comprising:
a. pymetrozine in an amount in the range of 5-70% by weight;
b. fipronil in an amount in the range of 1-80% by weight;
c. dinotefuran in an amount in the range of 0.5-85% by weight;
d. at least one agriculturally acceptable excipient.

3. The composition as claimed in claim 1, wherein the agriculturally acceptable adjuvant is selected from the group comprising of carrier(s), surfactant(s), binder(s), disintegrating agent(s), dispersants or dispersing agent(s), wetting agents, pH modifier(s), thickener(s), biocide(s), preservative(s), anti-freezing agent(s), defoamer(s), solvents, water soluble polymer, and/or stabilizer(s) or a combination thereof.

4. The composition as claimed in claim 3, wherein the dispersing agent is selected from the group comprising of Acrylic Co-Polymer Solution, Alcohols, C9-11-iso-, C10-rich, ethoxylated, and present in an amount in the range from 0.5 to 10.00 %w/w.

5. The composition as claimed in claim 3, wherein the anti-freezing agent is selected from the group comprising of glycols, mono-ethylene glycol, di-ethylene glycol, propylene glycol, polyethylene glycols, methoxy polyethylene glycols, polypropylene glycols, polybutylene glycols, glycerine and ethylene glycol present in an amount in the range from 0.5 to 10.00 %w/w.

6. The composition as claimed in claim 3, wherein the wetting agent is selected from the group comprising of alcohols, C9-11-iso-, C10-rich, ethoxylated present in an amount in the range from 0.5 to 10.00 %w/w.
7. The composition as claimed in claim 3, wherein the antifoaming agent is selected from the group comprising of silicon emulsion based anti-foam agents, Siloxane polyalkyleneoxide, Polydimethyl Siloxane, trisiloxane ethoxylates present in an amount in the range from 0.5 to 10.00 %w/w.

8. The composition as claimed in claim 3, wherein the water soluble polymer is selected from comprising of calcium lignosulfonate, sodium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate.

9. The composition as claimed in claim 8, wherein the water soluble polymer is present in an amount in the range of 1 to 15% w/w.

10. The composition as claimed in claim 1-9, wherein the composition is formulated as selected from Emulsifiable concentrate (EC), Emulsifiable granule (EG), Emulsion water-in-oil (EO), Emulsifiable powder (EP), Emulsion for seed treatment (ES), Emulsion oil-in-water (EW), Flowable Slurry (FS), Flowable Suspension(FS), Suspension Concentrate (SC), Suspension concentrate for direct application (SD), Suspo- emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Water soluble powder (SP ), Water dispersible powder for slurry seed treatment (WS), Water dispersible granules (WDG),Wettable powders (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), a mixed formulation of CS and SC (ZC) or A mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

11. A method of controlling insect comprising applying to the pests or the locus, an effective amount of a synergistic composition as claimed in claims 1-9.

12. A method for preparing synergistic insecticidal composition, comprising the steps of:
i) charging a pre feed mixing vessel with demineralized water (DM);
ii) adding and stirring the silicon defoamer with the premix;
iii) adding dispersion agent, wetting agent, and sodium lignosulfonate for 5 minutes;
iv) mixing and homogenizing the premix for 15 minutes after adding pymetrozine, fipronil, and dinotefuran;
v) milling the aforesaid premix and passing through bead mills until the necessary particle size (preferably below 10 microns) is not obtained;
vi) after milling, transferring the milled material to a second post feed vessel;
vii) incorporating the xanthan gum solution into the milled mixture and adding the biocide and remaining water quantity;
viii) combining and homogenizing the whole premix using a homogenizer for 20 minutes;
ix) if there are any lumps of xanthan gum present, increase the homogenization time for 5-10 minutes, and
x) packing the mixture into packs after passing through a normal sieve of 36 mesh if no lumps are observed.

13. The method as claimed in claim 12, wherein pymetrozine in step iv) is added in an amount in the range of 5-70% by weight, fipronil in an amount in the range of 1-80% by weight, and dinotefuran in an amount in the range of 0.5-85% by weight.